Hydrocarbon-soluble organoaluminum-magnesium complex

ABSTRACT

A novel process for polymerizng ethylene or a mixture of ethylene and another olefin is provided. In this process a novel catalyst having a very high activity per solid component of catalyst is used. Said catalyst is prepared by reacting a specific hydrocarbon-soluble organoaluminum-magnesium complex containing alkoxy, aryloxy, siloxy or siloxane groups, with one or more kinds of a titanium or vanadium compound having at least one halogen atom, and subsequently reacting the thus obtained hydrocarbon-insoluble reaction product (A) with a specified organoaluminum compound (B).

This is a division of Application of U.S. Ser. No. 579,639, filed May 5,1975 now U.S. Pat. No. 4,027,089, issued May 31, 1977.

DESCRIPTION OF THE INVENTION

This invention relates to processes for polymerization of ethylene andfor copolymerization of ethylene and another olefin. More particularly,it relates to a novel process for low-pressure polymerization ofethylene by means of a unique catalyst derived from anorganoaluminum-magnesium complex.

In connection with the process for low-pressure polymerization ofethylene in the presence of a catalyst consisting of a compound oftransition metals belonging to Groups IV-VIA of the Periodic Table andan organometallic compound of metals belonging to Groups I-III of thePeriodic Table, there have been developed and proposed numerouscatalysts since the discovery of Ziegler's catalyst. Most of these are,however, so deficient in catalytic activity that a step is necessary forremoving the catalyst from the polymer and this results in highercatalyst cost.

In recent years, extensive developments for highly active catalysts havebeen made with the view of omitting the catalyst removal step,simplifying the manufacturing process and reducing the catalyst cost.

The catalyst system known as high-activity catalyst is roughlyclassified into two groups. That is, the so-called supported catalystresulting from the synthesis of the Ziegler catalyst on a certain solidsurface; and a catalyst system prepared by combining a solid componentmade by reducing a titanium or vanadium compound with a specificorganometallic compound, and a specific organometallic activator. It isknown that many of the supported catalysts can provide much higheractivity employing as support a halide, hydroxyhalide, alkoxide ororganic acid salt or magnesium (for example, Japanese Patent PublicationNos. 13050-1968, 42039-1972 and 42137-1972 and Japanese laid open PatentApplication No. 5941-1972). As the catalyst system derived from aspecific organometal and a transition metal, these are known: a catalystprepared from a solid component prepared by reacting a Grignard reagentor a compound of RMgOR¹ made in an inert medium and a transition metalcompound (for example, West German laid open Application No. 2024558 andBritish Pat. No. 1299862); a catalyst made from a solid compoundprepared by reacting a specific organo-aluminum compound with a titaniumcompound (Japanese Patent Publication No. 26380-1972); and a catalystprepared from a solid compound containing titanium-and vanadium (forexample, Japanese Patent Publication Nos. 28708-1972 and 28709-1972).Each of these catalysts is provided with a satisfactory activity pertransition metal component but it cannot be said to be provided with asufficiently high activity per solid component. Accordingly, in case thecatalyst removal step is wholly omitted there will remain unsolveddifficulties such as deterioration of the polymer due to halogenremaining in the polymer and corrosion of the manufacturing equipment.

We continued intensive studies of catalysts having a high activity persolid component and have found that an appreciably highly activecatalyst is obtainable by combining a specific solid component made froma specific organoaluminum-magnesium complex and a titanium or vanadiumcompound, and an organoaluminum compound.

This invention resides in a process for polymerizing ethylene or amixture of ethylene and another olefin which comprises polymerizingethylene or a mixture of ethylene and another olefin in the presence ofa catalyst prepared by: reacting a hydrocarbon-solubleorganoaluminum-magnesium complex (i) represented by the general formula

    Al.sub.α Mg.sub.β X.sub.p Y.sub.q R.sub.r.sup.1 R.sub.s.sup.2

(wherein R¹ and R² each is a hydrogen atom or a hydrocarbon radicalhaving 1-10 carbon atoms; X and Y are the same or different radicals OR³or OSiR⁴ R⁵ R⁶ wherein R³ is a hydrocarbon radical having 1-10 carbonatoms; R⁴, R⁵ and R⁶ are each hydrogen atom or a hydrocarbon radicalhaving 1-12 carbon atoms; α and β are each a number more than zero, buthas relations of p + q + r + s = 3α + 2β and 0 < (p + q)/(α + β) ≦0.80), or a reaction product of a complex having the general formula ofAl.sub.α Mg.sub.β R_(r) ¹ R_(s) ² which corresponds to p + q = 0 in thegeneral formula (i), with a linear or cyclic siloxane compound (ii)having a constitutional unit ##STR1## (wherein R⁷ and R⁸ are eachhydrogen atom or a hydrocarbon radical having 1-10 carbon atoms) and oneor more kinds of a titanium or vanadium compound (iii) having at leastone halogen atom, and subsequently reacting the thus obtainedhydrocarbon-insoluble reaction product (A) with an organoaluminumcompound (B) represented by the general formula AlR_(m) ⁹ Z_(3-m)(wherein R⁹ is a hydrocarbon radical having 1-20 carbon atoms; Z isselected from the group consisting of hydrogen atom, halogen atom,alkoxy, aryloxy and siloxy groups; and m is a number in the range of2-3).

According to this invention, it is possible to attain as great anactivity as 30,000 g or more of polymer per solid component of catalyst,whereas, according to the patents concerning high-activity catalyststhat have already been disclosed (for example, the Japanese Patentsidentified hereinabove), the activity obtained is below 10,000. Acatalyst made from an organomagnesium compound and a transition metalcompound has already been disclosed (Japanese Patent Publication No.1546/1957). Since organomagnesium compounds are, however, insoluble ininert hydrocarbon solvents, there have not been achieved effective useof all the catalyst nor higher performance of activity. To overcomethese difficulties, attempts were made to use an organomagnesiumcompound in a specified form (West German laid open patent specificationNo. 2024558, Dutch Pat. No. 7103232 and British Pat. No. 1299862). Wealso have found that a new catalyst is obtainable by incorporating asolid reaction product which is synthesized from a hydrocarbon-solubleorganoaluminum-magnesium complex represented by the general formulaAl_(n) Mg_(m) R_(3n) R_(2m) ¹ wherein R and R¹ are hydrogen atom orhydrocarbon radicals, n and m are numbers of each greater than zero anda titanium or vanadium compound, with a hydrocarbon-solubleorganoaluminum compound and were granted Pat. No. 4,004,071. Thecatalyst of our previous patent has a much higher activity than those ofthe prior art cited above. As a result of extensive studies, we havealso found to our surprise that an organoaluminum-magnesium complexhaving an alkoxy, aryloxy, siloxy or siloxane group is soluble inhydrocarbon solvents. Then, we have achieved a super-active catalystderived from this peculiar complex. When alkoxy or aryloxy group isintroduced, in the molar range according to this invention, into adialkylmagnesium compound generally represented by R₂ Mg, there isformed a hydrocarbon-insoluble compound. It is assumed, therefore, thatsuch solubility results from a great change in its nature due to anorganoaluminum-magnesium complex formed.

If said unique aluminum-magnesium complex containing an alkoxy, aryloxy,siloxy or siloxane group is used to form a solid reaction product with atitanium or vanadium compound which is then combined with anorganoaluminum compound to make the specified catalyst forpolymerization of ethylene, the activity is increased with the increaseof the content of alkoxy, aryloxy, siloxy or siloxane groups anddecreased after passing a maximum value. It becomes easier to controlmolecular weight and the resultant polymer is narrower in molecularweight distribution and excellent in structural regularity. Thesuperiority of this catalyst will be described by way of Example 1 andComparative Example 1. MI appearing therein denotes melt index and wasmeasured at 190° C. and at 2.16 kg load in accordance with ASTM, D-1238.R represents a quotient obtained by dividing by MI the value determinedat 21.6 kg load under the condition for measurement of MI and is ameasure of moelcular weight distribution; the lower the value, thenarrower the molecular weight distribution. As is apparent from thecomparison between Example 1 and Comparative Example 1, the catalystaccording to the present invention also surpasses our prior catalysts.That is, it provides polymers having higher MI, i.e. lower molecularweight, although its activity is a little lower. Therefore, inmanufacturing polymers of the same molecular weight under a specifiedpolymerization pressure, it is possible to reduce the amount of hydrogenused and raise the partial pressure of ethylene in a relative manner andthus to increase the polymerization activity. The polymer is so narrowin molecular weight distribution that a sufficiently high strength canbe obtained even in a region of low molecular weight. This makes thepolymer suitable for the production of large articles by the injectionmolding method.

Further description will be made of organoaluminum-magnesium complex isrepresented by the general formula Al.sub.α Mg.sub.β X_(p) Y_(q) R_(r) ¹R_(s) ² wherein R¹, R², X and Y; α and β; p, q, r and s have all thesame meaning and/or relationship as above described.

The hydrocarbon radical represented by R¹ in the above-mentionedformula, having 1 to 10 carbon atoms, is alkyl, for example, methyl,ethyl, propyl, butyl, amyl, hexyl, octyl, decyl or the like and thehydrocarbon radical represented by R², having 1 to 10 carbon atoms, isalkyl or aryl, for example, methyl, ethyl, propyl, butyl, amyl, hexyl,octyl or phenyl as suitable radicals. As for the radicals OR³ and OSiR⁴R⁵ R⁶ represented by X and Y, the hydrocarbon radical R³ having 1-10carbon atoms is an alkyl, a cycloalkyl or an aryl radical and those arepreferable in which R³ is, for example, methyl, ethyl, propyl, butyl,amyl, hexyl, octyl, decyl, cyclohexyl or phenyl, R⁴, R⁵ and R⁶ arehydrogen atom or same or different hydrocarbon radicals having 1-10carbon atoms and as such hydrocarbons, for example, an alkyl radicalsuch as methyl, ethyl, propyl, butyl, hexyl or octyl, a cycloalkylradical such as cyclohexyl, methylcyclohexyl or the like, or an arylradical such as phenyl, naphthyl or the like. Illustrative siloxyradicals include, for example, methyldihydrosiloxy, dimethylhydrosiloxy,trimethylsiloxy, methylethylhydrosiloxy, methyldiethylsiloxy,triethylsiloxy, methylbutylhydrosiloxy, dimethylbutylsiloxy,methylphenylhydrosiloxy, ethylphenylhydrosiloxy,methylethylphenylsiloxy, triphenylsiloxy, α-naphthylphenylmethylsiloxy.The ratio of magnesium to aluminum β/α is particularly important inpreparing the active solid component of the present invention. In orderto synthesize a solid component having active structure, it is importantthat the complex used in the synthesis takes part in the reactioneffectively under the reaction condition. For that purpose, the presenceof the aluminum component suitable to stabilize the solution state isimportant. Too high a value of β/α and too lower a value reducesolubility. If β/α is low, the participation of the aluminum componentbecomes larger, resulting in reduction of activity. As is evident fromExamples 10-13 and Comparative Example 3 hereinafter described, apreferred range is 1-10 and a further preferable range is 2-6. Thecontent of X and Y radical, (p + q)/(α + β) is also important inattaining the effectiveness of the present invention. As is evident fromExamples 2-4 and Comparative Example 2 hereinafter described, in theregion of higher value of (p + q)/(α + β), activity is reduced.Accordingly, a preferred range is (p + q)/(α + β) ≦ 0.8. In order toobtain a polymer having a narrow molecular weight distribution, (p +q)/(α + β) is preferably in the range of 0.60-0.80. Thesiloxy-radical-containing complex is preferable because even if itscontent is increased, reduction of activity is low compared with thecomplex containing alkoxy or aryloxy radical. The said complex can bemade by: reacting an organo-aluminum compound represented by the generalformula AlR₃ (R is a hydrocarbon radical) and an organo-magnesiumcompound represented by the general formula MgR₂ ² or R² MgQ (R² is ahydrocarbon radical and Q is a halogen), and subsequently reacting theresultant hydrocarbon-soluble complex [Deutsches PatentamtAuslegeschrift 2232685 and Annalen des Chemie 605, 63 (1957)] and oxygenor an alcohol, silanol, aldehyde, ketone or ester of carboxylic acidunder moderate conditions; reacting an organomagnesium compoundrepresented by R₂ ¹ Mg and an alkoxy, aryloxy or siloxy aluminum orreacting alkoxy, aryloxy or siloxy magnesium represented by R² Mg(X) andAlR₃ ¹.

Description will be given of the siloxane compounds having the generalformula of ##STR2## The substituents R⁷ and R⁸ are hydrogen atom or sameor different hydrocarbon radicals having 1-10 carbon atoms. Amonghydrocarbon radicals, methyl, ethyl, propyl, butyl, hexyl, octyl,cyclohexyl, phenyl or the like is recommendable. These compounds can beused in the form of linear or cyclic dimeric or polymeric (greater thandimeric) compounds consisting of one or more kinds of the constitutionalunit. Illustrative compounds include symmetricdihydrotetramethyldisiloxane, hexamethyldisiloxane,pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane,polymethylhydrosiloxane (terminally blocked with methyl groups),polydimethylsiloxane, polyphenylhydrosiloxane (terminally blocked withmethyl group), polymethylphenylsiloxane or the like.

The reaction of organoaluminum-magnesium complex and siloxane is carriedout in an inert reaction medium (e.g. hexane, heptane, benzene ortoluene) at a temperature of -20°-150° C. with a reaction ratio of (Si -O)/(Mg + Al) in the range of 0.3-5, preferably 0.5-2. In this reaction,the forming of the bond of Si -- O -- M and the coordination bond of##STR3## (wherein M is Al or Mg) is confirmed by infrared spectrumanalysis and nuclear magnetic resonance spectrum analysis. It ispreferable that the ratio of (Si -- O -- M)/(Al + Mg) in the complex is0.8 or less, from the standpoint of activity. The above-mentionedcomplex bond is preferable because it does not influence the activity,narrows the molecular weight distribution and at the same time lowersthe chlorine content of the solid component [A].

The structure of the complex is not evident, but, as stated above, it isassumed that there results one or more complexes consisting of aluminumand magnesium components. This assumption is based on the fact that thereaction product made from R² Mg and oxygen or alcohol is insoluble ininert hydrocarbon solvents whereas said complex is soluble in thosemedia. It is also presumed that there occurs an exchange reactionbetween a hydrocarbon radical and an alkoxy or an aryloxy which isconnected with aluminum and magnesium.

The titanium or vanadium compound having at least one halogen atom[catalyst component (iii)] includes titanium tetrachloride, titaniumtetrabromide, titanium tetraiodide, ethoxytitanium trichloride,propoxytitanium trichloride, butoxytitanium trichloride,dibutoxytitanium dichloride, tributoxytitanium monochloride, vanadiumtetrachloride, vanadyl trichloride, monobutoxyvanadyl chloride,dibutoxyvanadyl monochloride; titanium and vanadium halides;hydroxyhalides; alkoxyhalides; and combinations thereof; particularlythose compounds containing three or more halogen atoms, are preferable.

The reaction process between the organoaluminium-magnesium complex andthe titanium or vanadium compound is extremely important for attainingthe effectiveness of the present invention and the reaction is effectedat a temperature up to 100° C., preferably below 20° C. in an inertreaction medium, e.g. aliphatic hydrocarbon such as hexane or heptane;aromatic hydrocarbon such as benzene, toluene or xylene; or alicyclichydrogen such as cyclohexane or methylcyclohexane. In order to achievehigh activity it is recommended that the reaction ratio of the twocatalyst components is 0.05-50 mols; especially 0.2-5 mols of theorganoaluminium-magnesium complex per mol of the titanium or vanadiumcompound. The number of mols for said organoaluminium-magnesium complexmeans the molar sum of aluminum and magnesium components. Taking as anexample AlMg₄ (OnC₄ H₉)₂.5 (C₂ H₅)₂.5 (n-C₄ H₉)₆, 722.3 gramscorresponding to the molecular weight of the above structural formula isequivalent to 5 mols. In order to attain high catalyst activity, thesimultaneous addition process in which two kinds of catalyst componentsare introduced simultaneously into the reaction zone is especiallysuitable. The hydrocarbon-insoluble reaction product may be directlyused, provided the reaction is complete. It is desirable, however, toisolate it from the reaction mixture to enhance the reproducibility ofpolymerization.

Further, by simultaneously reacting the reaction product thus obtained,with a halide of aluminium, silicon, tin, titanium or vanadium, acatalyst enabling production of a polymer having a more uniform particlesize and high bulk density can be synthesized.

As the organoaluminium compound (catalyst component B) according to thisinvention, there is used a compound or combined ones, denoted by thegeneral formula AlR_(m) ⁹ Z_(3-m). Hydrocarbon radical R⁹ containing1-20 carbon atoms is an aliphatic, aromatic or alicyclic hydrocarbon.The radical denoted by Z is a hydrogen, halogen atom, alkoxy, aryloxy orsiloxy radical and m is a number in the range 2-3. Recommended compoundsinclude, for example, triethylaluminum, tri-n-propylaluminum,tri-isopropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum,trihexylaluminum, trioctylaluminum, tridecylaluminum,tridodecylaluminum, trihexadecylaluminum, diethylaluminum hydride,di-isobutylaluminum hydride, diethylaluminum ethoxide,di-isobutylaluminum ethoxide, dioctylaluminum butoxide,di-isobutylaluminum octyloxide, diethylaluminum chloride,di-isobutylaluminum chloride, dimethylhydrosiloxyaluminum dimethyl,ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminumdiethyl, and combinations thereof.

Employing, in combination, the above alkylaluminum compound and theaforesaid hydrocarbon-insoluble solid results in a highly activecatalyst. To obtain an extremely high catalytic activity, it ispreferable to use especially a trialkylaluminum or dialkylaluminumhydride. When incorporating group Z, which is electronegative, intrialkylaluminum or dialkylaluminum hydride, the resultant polymer tendsto decrease in activity but with the characteristic polymerizationbehavoir. Thus it is possible to make more useful polymers underhigh-activity conditions. As an example, introducing an alkoxy groupaffords easier control of molecular weight. The reaction betweencatalyst components (A) and (B) in accordance with the invention may beconducted by adding said both components to the polymerization systemand under the polymerization condition, or otherwise in advance ofpolymerization. The reaction ratio of the components is preferably1-3,000 m mols of component (B) per gram of component (A).

As the polymerization method there are available the usual suspension-,solution- and gas phase polymerizations. In cases of suspension orsolution polymerization processes, the catalyst is let into the reactorwith a polymerization medium, e.g. aliphatic hydrocarbon such as hexaneor heptane; aromatic hydrocarbon such as benzene, toluene or xylene; oralicyclic hydrocarbon such as cyclohexane or methylcyclohexane. Then,ethylene is added up to 1-50 kg/cm² in an inert atmosphere and allowedto polymerize at room temperature to 150° C. On the other hand, in caseof gas phase polymerization, it is possible to carry out thepolymerization under the condition of 1-50 kg/cm² pressure of ethyleneat a temperature from room temperature to 120° C. by using a proceduresuch as fluidized bed, moving bed or mixing with a stirrer in order togive better contact of ethylene with the catalyst. The catalyst can beadded as it is, in the form of a solution or dispersion in hydrocarbonas mentioned above. In order to control the molecular weight of polymer,it is also possible to add hydrogen, a hydrocarbon halide or anorganometallic compound which is liable to bring about chain transfer.

The catalyst according to this invention enables copolymerization withmono-olefins such as propylene, butene-1 or hexene-1, as well aspolymerization of propylene with high efficiency.

The following examples illustrate but do not limit the invention.Symbols MI and R therein have the same meaning as above-mentioned.Catalyst efficiency is expressed as gram(s) of polymer per gram of solidcomponent per hour per kg/cm² of ethylene pressure.

EXAMPLE 1

(1) Synthesis of the organoaluminum-magnesium complex

In a 500 ml flask, were placed 13.80 g of di-n-butylmagnesium and 2.85 gof triethylaluminum together with 200 ml of n-heptane. The mixture wasreacted, with stirring, at 80° C. for 2 hours. Thus a complex having thecomposition corresponding to AlMg₄ (C₂ H₅)₃ (n-C₄ H₉)₈ was synthesized.This solution was cooled down to 10° C. and 50 ml of a solution of 50 mmols n-octanol in n-heptane was added, with cooling gradually, dropwisefor one hour. Thus an organo-aluminum-magnesium complex was synthesized.One portion of this solution was separated and oxidized by dry air, thenhydrolyzed to convert the alkyl and alkoxy groups into their alcohols.The final product was analyzed by gas chromatography. From theanalytical values based on ethanol, n-butanol and n-octanol, thecomposition proved to be AlMg₄ (On-C₈ H₁₇)₂.02 (C₂ H₅)₂.70 (n-C₄H₉)₆.28.

(2) Synthesis of hydrocarbon-insoluble solid component

Oxygen and moisture inside a 500 ml flask equipped with 2 droppingfunnels were removed by substituting with dry nitrogen, 160 ml ofn-heptane was added thereto and cooled to -20° C. Then 80 ml ofn-heptane solution containing 40 m mol of the above-mentioned complexand 80 ml of n-heptane solution containing 40 m mol of titaniumtetrachloride were separately introduced in the dropping funnels. Boththe components were simultaneously added with stirring at -20° C. for 2hours and further reacted at this temperature for three hours. Resultinghydrocarbon-insoluble solid was isolated, washed with n-heptane anddried to give 10.8 g of the solid product.

(3) Polymerization reaction

In a 5 liter autoclave having been evacuated and nitrogen-substitutedwere placed 5 mg of the hydrocarbon-insoluble reaction product made instep (2) and 3.0 m mol of tri-isobutylaluminum plus 3 liter of n-heptanepreviously dehydrated and degassed. While the inner temperature of theautoclave was kept at 85° C., there was added hydrogen up to 3.0 kg/cm²gauge pressure followed by ethylene up to 10.0 kg/cm² total gaugepressure. With this condition the polymerization was performed for anhour. There was obtained 1.02 kg of polymer; MI, 2.76 and R, 31. Thecatalyst efficiency was 29,000.

COMPARATIVE EXAMPLE 1

The synthesis of catalyst and the polymerization were conducted just asin Example 1 except that organo-aluminum-magnesium complex of thecomposition AlMg₄ (C₂ H₅)₃ (n-C₄ H₉)₈ made in Example 1 was used toprepare its hydrocarbon-insoluble reaction product. There was obtained1.25 kg of polymer; MI, 0.85 and R, 46. The catalyst efficiency was35,700.

EXAMPLE 2-4, COMPARATIVE EXAMPLE 2

A hydrocarbon-insoluble solid was synthesized similarily as in Example 1except that organo-aluminum-magnesium complexes indicated in Table 1were used. Polymerization was carried out under the same conditions asthese of Example 1 by using 5 mg of said solid and 3.0 m mol oftriisobutylaluminum.

                                      Table 1                                     __________________________________________________________________________                               Polymerization result                                                         Yield                                                                             Catalyst                                       Examples                                                                             Organoaluminum-magnesium complex                                                                  kg  efficiency                                                                         MI R                                      __________________________________________________________________________    2      AlMg.sub.4 (OC.sub.8 H.sub.17).sub.0.60 (C.sub.2 H.sub.5).sub.2.85            (n-C.sub.4 H.sub.9).sub.7.55                                                                      1.32                                                                              37,600                                                                             1.25                                                                             37                                     3      AlMg.sub.4 (OC.sub.8 H.sub.17).sub.1.50 (C.sub.2 H.sub.5).sub.2.75            (n-C.sub.4 H.sub.9).sub.6.75                                                                      0.935                                                                             26,700                                                                             2.95                                                                             29                                     4      AlMg.sub.4 (OC.sub.8 H.sub.17).sub.3.85 (C.sub.2 H.sub.5).sub.2.50            (n-C.sub.4 H.sub.9).sub.4.65                                                                      0.686                                                                             19,600                                                                             5.43                                                                             27                                     Comparative                                                                   Example 2                                                                            AlMg.sub.4 (OC.sub.8 H.sub.17).sub.5.05 (C.sub.2 H.sub.5).sub.1.95            (n-C.sub.4 H.sub.9).sub.4.00                                                                      0.189                                                                              5,200                                                                             7.20                                                                             26                                     __________________________________________________________________________

EXAMPLE 5

In the same manner as in Example 1, organo-aluminium-magnesium complexof the composition AlMg₆ (OiC₄ H₉)₄.55 (C₂ H₅)₂.60 (nC₄ H₉)₇.85 wasprepared by the use of triethylaluminum, di-n-butylmagnesium andisobutanol. Then, 40 m mol of titanium tetrachloride and 80 m mol of theabove complex were reacted at 0° C. for 3 hours. Using 5 mg of theresultant hydrocarbon-insoluble solid and 6.0 m mol of trihexylaluminum,the polymerization was conducted as in Example 1. There was obtained0.98 kg of polymer; MI, 3.50 and R, 30. The catalyst efficiency was27,900.

EXAMPLE 6

In the same way as in Example 1, organo-aluminum-magnesium complex ofthe composition AlMg₆ (OnC₃ H₇)₂.10 (C₂ H₅)₂.75 (n-C₄ H₉)₁₀.15 wasprepared by the use of triethylaluminum, di-n-butylmagnesium andn-propanol. Then 40 m mol of titanium tetrachloride and 32 m mol of thiscomplex were reacted at 10° C. for 4 hours. Using 5 mg of the resultanthydrocarbon-insoluble solid and 6.0 m mol of trioctylaluminum, thepolymerization was carried out as in Example 1. There was obtained 0.95kg of polymer; MI, 1.65 and R, 35. The catalyst efficiency was 27,100.

EXAMPLE 7

In the same manner as in Example 1, organo-aluminum-magnesium complex ofthe composition AlMg₂ (OnC₆ H₁₃)₁.35 (i-C₄ H₉)₂.65 (n-C₄ H₉)₃.0 wasprepared by the use of triisobutylaluminum, di-n-butylmagnesium andn-hexylalcohol. Then, 40 m mol of a 1:1 by mole mixture of titaniumtetrachloride and monobutoxy-titanium trichloride and 40 m mol of theabove complex were reacted at 0° C. for 4 hours. Using 5 mg of theresultant hydrocarbon-insoluble solid and 3.0 m mol oftriisobutylaluminum, the polymerization was carried out as in Example 1.There was obtained 0.65 kg of polymer; MI, 3.60 and R, 32. The catalystefficiency was 18,600.

EXAMPLE 8

In the same way as in Example 1, organo-aluminum-magnesium complex ofthe composition AlMg₃ (OC₂ H₅)₁.40 (nC₃ H₇)₂.70 (nC₆ H₁₃)₄.90 was madeby the use of tri-n-propylaluminum, di-n-hexylmagnesium and ethanol.Then, 40 m mol of vanadium tetrachloride and 40 m mol of this complexwere reacted at -10° C. for 3 hours. In a 5-liter autoclave having beenevacuated to vacuum and nitrogen-substituted were placed 5 mg of theresultant hydrocarbon-insoluble solid and 3.0 m mol oftri-isobutylaluminum together with 3 liters of n-heptane previouslydehydrated and degassed. While the inner temperature of the autoclavewas kept at 85° C., there was added hydrogen up to 2.0 kg/cm² gaugepressure followed by ethylene up to 6.0 kg/cm² total gauge pressure. Thepolymerization was conducted for one hour while additional ethylene wasadded to maintain the total gauge pressure at 6.0 kg/cm². There wasobtained 0.42 kg of polymer; MI, 1.89 and R, 34. The catalyst efficiencywas 21,000.

EXAMPLE 9

In the same way as in Example 1, organo-aluminum-magnesium complex ofthe composition AlMg₅ (On-C₄ H₉)₃.0 (n-C₄ H₉)₁₀ was prepared by reacting2.46 g of tri-n-butoxyaluminum and 6.90 g of di-n-butylmagnesium at 80°C. for 3 hours. Then, 40 m mol of this complex and 40 m mol of vanadyltrichloride were reacted at -20° C. for 4 hours. Using as catalystcomponent 5 mg of the resultant hydrocarbon-insoluble solid and 3.0 mmol of tri-decylaluminum, the polymerization was performed as in Example5. There was obtained 0.46 kg of polymer; MI, 2.15 and R, 33. Thecatalyst efficiency was 23,000.

EXAMPLES 10-14 AND COMPARATIVE EXAMPLE 3

A hydrocarbon-insoluble solid was obtained as in Example 1 by reactingthe organoaluminum-magnesium complex indicated in Table 2 at -30° C. for4 hours. By using 5 mg of this solid and 3 m mol of trioctylaluminum,polymerization was carried out as in Example 8, whereby the result shownin the table was obtained.

                                      Table 2                                     __________________________________________________________________________                                Polymerization result                                                         Yield                                                                             Catalyst                                      Examples                                                                             Organoaluminum-magnesium complex                                                                   kg  efficiency                                                                         MI R                                     __________________________________________________________________________    10     AlMg.sub.8 (OnC.sub.4 H.sub.9).sub.4.53 (C.sub.2 H.sub.5).sub.2.65            (n-C.sub.4 H.sub.9).sub.11.82                                                                      0.374                                                                             18,700                                                                             3.13                                                                             28                                    11     AlMg.sub.6 (OnC.sub.4 H.sub.9).sub.3.46 (C.sub.2 H.sub.5).sub.2.72            (n-C.sub.4 H.sub.9).sub.8.82                                                                       0.530                                                                             26,500                                                                             3.52                                                                             28                                    12     AlMg.sub.2 (OnC.sub.4 H.sub.9).sub.1.52 (C.sub.2 H.sub.5).sub.2.80            (n-C.sub.4 H.sub.9).sub.2.68                                                                       0.450                                                                             22,500                                                                             2.87                                                                             29                                    13     AlMg(OnC.sub.4 H.sub.9).sub.1.05 (C.sub.2 H.sub.5).sub.2.75                   (n-C.sub.4 H.sub.9).sub.1.20                                                                       0.352                                                                             17,600                                                                             4.05                                                                             32                                    14     AlMg.sub.4 (OnC.sub.4 H.sub.9).sub.2.05 (C.sub.2 H.sub.5).sub.2.02            (C.sub.10 H.sub.33).sub.6.93                                                                       0.390                                                                             19,500                                                                             2.52                                                                             32                                    Comparative                                                                   example 3                                                                            Al.sub.2 Mg(OnC.sub.4 H.sub.9).sub.1.32 (C.sub.2 H.sub.5).sub.5.66            (n-C.sub.4 H.sub.9).sub.1.02                                                                       0.150                                                                              7,500                                                                             3.44                                                                             35                                    __________________________________________________________________________

EXAMPLE 15

Using 5 mg of the hydrocarbon-insoluble solid component made in Example1 and 6.0 m mol of organo-aluminum component of the composition Al(i-C₄H₉)₂.50 (OC₂ H₅)₀.50, the polymerization was carried out as inExample 1. The polymer weighed 0.92 kg; MI, 5.20 and R, 30. The catalystefficiency was 26,300.

EXAMPLE 16

Using 5 mg of the hydrocarbon-insoluble made in Example 1 and 6.0 m molof organo-aluminum component of the composition Al(i-C₄ H₉)₂.50 Cl₀.50the polymerization was carried out as in Example 1. The polymer weighed0.84 kg; MI, 3.80 and R, 31. The catalyst efficiency was 24,000.

EXAMPLE 17

In the same way as in Example 9, organo-aluminum-magnesium complex ofthe composition AlMg₂ (OC₂ H₅)₁.0 (C₂ H₅)₂.0 (n-C₄ H₉)₄.0 wassynthesized from diethylaluminum ethoxide and di-n-butylmagnesium. 40 mmol of titanium tetrachloride and 40 m mol of this complex were reactedat -5° C. for 4 hours. The polymerization was carried out as in Example1 except that 5 mg of the resultant hydrocarbon-insoluble solid and 3.0m mols of tri-isobutylaluminum were used together with anethylene-propylene mixture containing 3% of propylene instead ofethylene. The polymer weighed 1.26 kg; MI, 7.50 and R, 26. The catalystefficiency was 36,000.

EXAMPLE 18

The polymerization was performed as in Example 17 except that anethylene-butene-1 mixture gas containing 2% of butene-1 was used insteadof an ethylene-propylene mixture gas. The polymer weighed 1.08 kg; MI,9.75 and R, 27. The catalyst efficiency was 30,500.

EXAMPLE 19-26

A hydrocarbon-insoluble solid was synthesized as in Example 1 byreacting (A) organoaluminum-magnesium complexes which are shown in Table3 and obtained by reacting dialkylmagnesium and siloxyaluminum compoundas in Example 1, with (B) titanium tetrachloride with a mol ratio of A:Bof 1:1. For the synthesis of the hydrocarbon-insoluble solid, inExamples 19-24, addition of the two components was carried out at -10°C. for 2 hours and a further reaction was carried out at 5° c. for 2hours, and in Examples 25-26, addition of the two compounds was carriedout at -20° C. for 2 hours and a further reaction was carried out at 10°C. for 2 hours. By using 5 mg of this solid and organoaluminum compoundshown in Table 3, polymerization was carried out similarly as in Example8 whereby results shown were obtained. The organoaluminum-magnesiumcomplex in Example 26 was synthesized by the reaction of AlMg₃ (C₂ H₅)₃(n-C₄ H₉)₆ and trimethylsilanol.

                                      Table 3                                     __________________________________________________________________________                                                      Polymerization result                                                                 Catalyst            Ex-                             Organoaluminum compound                                                                        Yield    ef-                 ample                                                                              Organoaluminum-magnesium complex                                                                         (amount used m mol)                                                                            g   MI R ficiency            __________________________________________________________________________    19  AlMg.sub.2 (n-C.sub.4 H.sub.9).sub.2 (n-C.sub.3 H.sub.7).sub.4                [OSi(CH.sub.3).sub.2 n-C.sub.4 H.sub.9 ]                                                                  Al(i-C.sub.4 H.sub.9).sub.3                                                                (1.5)                                                                             485 2.30                                                                             33                                                                              24,300              20  AlMg.sub.6 (C.sub.2 H.sub.5)(n-C.sub.4 H.sub.9).sub.12 (OSi . H .             CH.sub.3 . C.sub.2 H.sub.5).sub.2                                                                         Al(C.sub.2 H.sub.5).sub.2.5 (OC.sub.2                                         H.sub.5).sub.0.5                                                                           (3.0)                                                                             560 4.21                                                                             31                                                                              28,000              21  AlMg.sub.3 (C.sub.2 H.sub.5)(n-C.sub.4 H.sub.9).sub.6 (OSi . H .              CH.sub.3 . C.sub.2 H.sub.5).sub.2                                                                         Al(i-C.sub.4 H.sub.9).sub.2.5 Cl.sub.0.5                                                   (3.0)                                                                             515 3.96                                                                             29                                                                              25,800              22  AlMg.sub.2 (C.sub.2 H.sub.5).sub.2 (n-C.sub.5 H.sub.11).sub.4 (OSi .          H . C.sub.2 H.sub.5 . C.sub.6 H.sub.6)                                                                    Al(n-C.sub.6 H.sub. 13).sub.3                                                              (3.0)                                                                             460 3.06                                                                             34                                                                              23,000              23  AlMg.sub.2 (C.sub.2 H.sub.5).sub.4 (n-C.sub.3 H.sub.7).sub.2 (OSi . H         . CH.sub.3 n . C.sub.3 H.sub.7)                                                                           Al(n-C.sub.12 H.sub.25).sub.3                                                              (3.0)                                                                             490 1.96                                                                             33                                                                              24,500              24  AlMg(i-C.sub.4 H.sub.9).sub.2 (n-C.sub.6 H.sub.13).sub.2 (OSi . H .           CH.sub.3 . n . C.sub.4 H.sub.9)                                                                           Al(n-C.sub.8 H.sub.17).sub.3                                                               (3.0)                                                                             385 4.51                                                                             30                                                                              19,300              25  AlMg.sub.3 (C.sub.2 H.sub.5).sub.1.50 (n-C.sub.4 H.sub.9).sub.6.0             (OSi . H . CH.sub.3 . C.sub.2 H.sub.5).sub.1.50                                                           Al(i-C.sub.4 H.sub.9).sub.3                                                                (1.5)                                                                             530 3.25                                                                             32                                                                              26,500              26  AlMg.sub.3 (C.sub.2 H.sub.5).sub.1.65 (n-C.sub.4 H.sub.9).sub.4.20            [OSi(CH.sub.3).sub.3 ].sub.3.15                                                                           Al(i-C.sub.4 H.sub.9).sub.2.5 Cl.sub.0.5                                                   (3.0)                                                                             464 5.28                                                                             28                                                                              23,200              __________________________________________________________________________

EXAMPLES 27 to 31

Di-n-butylmagnesium and siloxyaluminum of the composition Al(C₂H₅)(OSi.H.CH₃.C₂ H₅)₂ were reacted as in Example 1 to prepare itsorgano-aluminum-magnesium complex. This complex and the titanium orvanadium compound shown in Table 2 were reacted in the same way underthe corresponding condition shown in the Table. Utilizing 5 mg of theresultant hydrocarbon-insoluble solid and the alkylaluminum compoundshown, the polymerization was conducted under the same condition as inExample 1. The results are also given in that Table.

                                      Table 4                                     __________________________________________________________________________    Hydrocarbon-insoluble solid                                                                      temp.                                                                   mol   x    Organoaluminum                                                                          Polymerization result                           Titanium,                                                                              ratio time compound           Catalyst                           Ex- vanadium,                                                                              Al + Mgl                                                                            (° C.)                                                                      (Amount used                                                                            Yield    ef-                                ample                                                                             compound Ti or V                                                                             (hr) m mol)    g   ML R ficiency                           __________________________________________________________________________        A 2:1 mixture of                                                          27  TiCl.sub.4 and TiCl.sub.3                                                              1/1   φ × 4                                                                    Al(n-C.sub.3 H.sub.7).sub.3                                                          (1.5)                                                                            345 5.20                                                                             28                                                                              17,300                                 (OnC.sub.4 H.sub.9)                                                       28  VCl.sub.4                                                                              1/1   -20 × 4                                                                      Al(n-C.sub.4 H.sub.9).sub.3                                                          (1.5)                                                                            585 2.21                                                                             36                                                                              29,300                                 A 2:1 mixture of                                                          29  TiCl.sub.4 and VoCl.sub.3                                                              1/1    -5 × 4                                                                      Al(i-C.sub.3 H.sub.7).sub.3                                                          (1.5)                                                                            520 3.45                                                                             31                                                                              26,000                             30  TiCl.sub.4                                                                             2/1   -30 × 4                                                                      Al (i-C.sub.4 H.sub.9).sub.2 H                                                       (1.5)                                                                            565 2.90                                                                             32                                                                              28,300                             31  TiCl.sub.4                                                                             0.7/1 -10 × 4                                                                      Al (C.sub.2 H.sub.5).sub.2 H                                                         (1.5)                                                                            510 3.25                                                                             30                                                                              25,500                             __________________________________________________________________________

EXAMPLES 32-37

(1) Reaction of organoaluminum-magnesium complex and siloxane

Fifty ml heptane solution containing the organoaluminum magnesiumcomplex, synthesized as in Example 1, in a concentration of 1.0 mol/lwas reacted in a 200 ml flask with 50 ml heptane solution containing asiloxane compound in a concentration of 0.5-2.0 mol/l based upon Si--O.

With regard to organoaluminum-magnesium complex, soloxane and reactioncondition, those indicated in Table 5 are used.

The measurement of the bond of Si--O--M (wherein M is aluminum ormagnesium) was carried out by concentrating the above-mentioned reactionproduct and determining the amount of gas generated at the time ofdecomposition with water.

(2) Synthesis of hydrocarbon-insoluble solid

By using the same method as that of Example 1 and under the conditionsof Table 5, the synthesis of hydrocarbon-insoluble solid was carriedout.

(3) Polymerization

Five mg of hydrocarbon-insoluble solid synthesized in (2), variousaluminum components and dehydrated degassed hexane were introduced in a1.5 l autoclave having been evacuated and then filled with nitrogen.While the inside temperature of the autoclave was maintained at 85° C.the pressure of hydrogen and ethylene were brought to the valuesindicated in Table 5 and the total pressure formed together with hexanevapor pressure was set to 4.7 kg/cm² gauge. Polymerization was carriedout for one hour while holding the total pressure of 4.7 kg/cm² gauge byfeeding ethylene, whereby the result shown in Table 5 was obtained.

                                      Table 5                                     __________________________________________________________________________    Caatalyst                                                                     Hydrocarbon-insoluble solid                                                    Organoaluminum-magnesium complex siloxane               Composi              reaction product                         Ti or                                                                             Ti/         Composi-                 Organoalumin m                       v   Al + Mg                                                                             Temp  tion 90 by           Ex- magnesium          Si-O/ temp. x                                                                             Si-O-M                                                                              com-                                                                              (mol  x     weight               ample                                                                             complex  Siloxane  Al + Mg                                                                             time  /Al + Mg                                                                            pound                                                                             ratio time  Ti Cl                __________________________________________________________________________        AlMg.sub.6 (C.sub.2 H.sub.5).sub.3                                                     Syn. tetra-     Hr                                                   AlMg.sub.6 (C.sub.2 H.sub.5).sub.3                                                     methyl-   1.0   0° C. × 1/2                                                            0.17  TiCl.sub.4                                                                        1/1    5° C. ×                                                         4     13.2                                                                             37.5              32  (n-C.sub.4 H.sub.9).sub.12                                                             dihydro-                                                                      disiloxane                                                                    Methylhydro-    ° C. Hr                                       AlM g.sub.2 (i-C.sub.4 H.sub.9).sub.3                                                  polysiloxane                                                                            1.0   100 ×  5                                                                      0.78  TiCl.sub.4                                                                        1/1    5° C. ×                                                         4     12.5                                                                             38.9              33  (n-C.sub.4 H.sub.9).sub.4                                                              viscosity 30                                                                  Centistokes 30° C.                                                     methylpoly-     ° C. Hr                                       AlMg.sub.4 (C.sub.2 H.sub.5).sub.3                                                     siloxane  0.8   100 × 10                                                                      0.25  TiCl.sub.4                                                                        2/1   10° C. ×                                                         4     14.1                                                                             37.2              34  (n-C.sub.3 H.sub.7).sub.8                                                              viscosity 50                                                                  Centistokes 30° C.                                                     Cyclic          Hr                                                   AlMg.sub.6 (C.sub.2 H.sub.5).sub.3                                                     methyl-   1.0   80° C. ×≡5                                                       0.72  TiCl.sub.4                                                                        1/1    5° C. ×                                                         4     11.2                                                                             39.2              35  (n-C.sub.4 H.sub.9).sub.12                                                             hydrotetra-                                                                   siloxane                                                         36  "        "         "     "     0.72  VCl.sub.4                                                                         1/1    0° C. ×                                                         4     12.5                                                                             43.1                           Syn. tetra-     Hr                                                   AlMg.sub.6 (C.sub.2 H.sub.5).sub.3                                                     methyl-   1.0   0° C. × 1/2                                                            0.17  TiCl.sub.4                                                                        1/1    5° C. ×                                                         4     13.2                                                                             37.5              37  (n-C.sub.4 H.sub.9).sub.12                                                             dihydro-                                                                      disiloxane                                                       __________________________________________________________________________

    __________________________________________________________________________    Catalyst                                                                      Organoaluminum                                                                compounds   Polymerization pressure                                                                   Polymerization result                                  (amount used                                                                             Hydrogen                                                                             Ethylene                                                                           Yield                                                                             Catalyst                                          m mol)      kg/cm.sup.2                                                                          kg/cm.sup.2                                                                        g   efficiency                                                                          MI R                                        __________________________________________________________________________    Al(i-C.sub.4 H.sub.9).sub.3                                                               1.3    2.7  327 24,200                                                                              6.1                                                                              30                                                (0.5)                                                                Al(C.sub.8 H.sub.17).sub.3                                                                1.0    3.0  325 21,700                                                                              4.5                                                                              27                                                (2.0)                                                                Al(n-C.sub.3 H.sub.7).sub.3                                                               1.0    3.0  264 17,600                                                                              3.5                                                                              25                                                (1.0)                                                                Al(i-C.sub.4 H.sub.9).sub.3                                                               1.3    2.7  286 21,200                                                                              6.8                                                                              27                                                (0.5)                                                                Al(C.sub.2 H.sub.5).sub.2.5 (OC.sub.2 H.sub.5).sub.0.5                                    1.3    2.7  259 19,200                                                                              7.2                                                                              26                                                (2.0)                                                                Al(i-C.sub.4 H.sub.9).sub.3                                                               0.7    3.3  343 29,700                                                                              2.1                                                                              26                                                (0.5)                                                                __________________________________________________________________________

What we claim is:
 1. A hydrocarbon-soluble organoaluminum-magnesiumcomplex of the formula

    Al.sub.α Mg.sub.β X.sub.p Y.sub.q R.sub.r.sup.1 R.sub.s.sup.2

wherein R¹ is a hydrogen atom or an alkyl radical having 1 to 10 carbonatoms, R² is a hydrogen atom, or an alkyl or aryl radical having 1 to 10carbon atoms, X and Y each independently is OR³ or OSiR⁴ R⁵ R⁶, R³ is analkyl, cycloalkyl or aryl radical having 1 to 10 carbon atoms, R⁴, r⁵and R⁶ each independently is a hydrogen atom or an alkyl, cycloalkyl oraryl radical having 1 to 12 carbons atoms, α and β each independently isa number more than zero and β/α is from 1 to 10, p + q + r + s = 3α +2β, and 0 < (p+q)/(α+β)≦0.8.
 2. A hydrocarbon-solubleorganoaluminum-magnesium complex of the formula

    Al.sub.α Mg.sub.β R.sub.r.sup.1 R.sub.s.sup.2 (OR.sup.3).sub.p

wherein R¹ is an alkyl radical having 1 to 10 carbon atoms, R² is analkyl or aryl radical having 1 to 10 carbon atoms, R³ is an alkyl,cycloalkyl or aryl radical having 1 to 10 carbon atoms, α and β eachindependendently is a number more than zero, β/α is from 1 to 10,p+r+s=3α+2β, and < p/(α+β) ≦ 0.80.
 3. A hydrocarbon-solubleorganoaluminum-magnesium complex of the formula

    Al.sub.60 Mg.sub.62 R.sub.r.sup.1 R.sub.s.sup.2 (OSiR.sup.4 R.sup.5 R.sup.6).sub.p

wherein R¹ is an alkyl radical having 1 to 10 carbon atoms, R² is analkyl or aryl radical having 1 to 10 carbon atoms, R⁴, r⁵ and R⁶ eachindependently is a hydrogen atom or an alkyl, cycloalkyl or aryl radicalhaving 1 to 12 carbon atoms, α and β each independently is a number morethan zero, β/α is from 1 to 10, p+r+s=3α+2β, and 0 < p/(α+β) ≦ 0.80.